Azodyestuffs



Patented May 17, 1938 2,117,731

UNITED STATES PATENT OFFICE AZODYESTUFFS Theodor Kollmann, Leverkusen, and Eugen Glietenberg, Leverkusen-I. G.-Werk, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation oi Delaware No Drawing. Application November 11, 1936, Serial No. 110,278. In Germany December 18,

13 Claims. (C1. 8-6) The present invention relates to water insoluble cyclic bases or cyanamide or cyanamide carazo dyestuffs and to printing preparations suitboxylic acid (compare U. S. Patents 1,858,623, able for the manufacture of the said dyestuffs 1,874,524, 1,867,088, 1,871,850, 1,879,424, 1,882,560, by a printing process, more particularly our in- 1,882,562, 1,979,327, 1,982,681), and by developvention relates to water insoluble azo dyestuffs ing the dyestufi in the customary manner, e. g. 5 which may be represented by the general by hanging, steaming or treating with dilute acids formula; or steam containing an acid (compare U. S. Pat- R--N=NR'-N==NR ents 1,880,522, 1,882,556, 1,893,991, 2,035,518). In this manner in general brown shades of good 10 fastness properties are obtained. 10

In the said formula R stands for an aromat c According to a further feature of the invention radical which may bear further azo groups, for for producing the new water insoluble azo dyeexample for the radical of the benzene series, of stuffs by a printing process preparations consistthe naphthalene series, of the diphenyl series and mg of the above-named azo dyestuffs and arylthe like, R stands for a radical of the benzene nitrosamines or aryldiazoaminoor -imino corn- 15 serie p l of p in wi e. w ch is u pounds, soluble in water or an alkaline medium, itu ed in a p s i n me a to Y y n amino r have proved particularly suited. (Compare U. s.

a hy r xy r p, y the y xy roup, how- Patents 1,882,561, 1,915,734). ever, only when Y stands for NH, R. stands for The metal containing ortho-hydroxyazo dyethe radical of a diazotized aromatic amine of the tuff ed a starting materials can also be ob- 20 kind generally used in the manufacture of ice tained from ortho-halogen amines or orthocolors, X s ands for an xy n m r the group alkoxy amines as diazotization components with CO0, Y stands for an oxygen atom or the group replacement of the halogen or splitting up of the NH, Me stands for a metallic atom, capable of alkoxy groups.

yielding azo dyestufi complex compou d and The invention is illustrated by the following wherein the bridge X-Me-Y is attached to the examples: nuclei in positions ortho to the azo bridge, it being Example 1 self understood that groups inducing solubility A cotton tissue is printed with a printing color, in water such as the sulfonic acid group and the containing in 1000 grams:

0 carboxylic acid group, are excluded as substitu- 28 grams of the diazoimino compound from 30 ents.

The process of an Eacture of the dyestuffs diazotized 4-chloro 2 anisidine and sarcosine,

accordin to the invention is by coupling espe- 32 15 of the Copper 00 plex co I H d of g the monoazo dyestufi from 4-chloro-2-diazophecially on the fiber, metal complex compounds of 35 the azo dyestuffs from meta-aminophenol, metazg gg i fi coupled in an acetic 35 phenylenediamine or the substitution products 0 thereof, capable of coupling twice, and orthogl g grigi iggz f i zggf hydr'oxyor ortho-carboxydiazo compounds, the 500 grams neutral Sgamh tljagwanth azo dyestuffs containing no further solubilizing thickener the remainder hem water 40 groups, with diazo compounds suitable for the dri d t f 51m t 40 manufacture of ice colors. The process may be e S gamed or nutes i s 8am containing effected in the manner generally used in the manacetic and i formic acid rinsed soaped' again ufacture of ice colors by impregnating the fiber lf'msed and dnedt Avery deep brown or good astness properties is obtained.

with the azo dyestuffs containing metal referred to above and further developing the dyeing with f fi f z cozresponds to the following 45 suitable diazo compounds.

A particular method of effecting the process is by bringing the said coupling component on the O C1 fiber together with an arylnitrosamine suitable for the manufacture of ice colors (compare U. S. N=N 50 P. 1,915,734) or a suitable aryldiazo-aminoor b -imino compound soluble in water or an alkaline 1 1 medium, as obtainable by the condensation of Instead of coupling the meta-aminophenol diazo compounds with primary aliphatic or arodyestuff in an acid medium also an alkaline mematic, secondary aliphatic aromatic or heterodium can be used. 55

' Example 2 A cotton tissue is printed with a. printing color containing in 1000 grams: 1

28 grams of the diazoimino compound from diazotized 4-chloro-2-anisidine and sarcosine,

31 grams of the copper complex compound of the monoazodyestufi from 4-chlorodiazophen0l and meta-phenylene diamine, I

50 grams of glycolmonoethylether,

500 grams of a neutral starch tragacanth thickener, the remainder being water,

and developed as described in Example 1. A reddish brown is thus obtained.

The dyestufi' corresponds to the following Example 3 A cotton tissue is printed with a printing color containing in 1000 grams:

The dyestufi corresponds to the following formula:

A deep formula: O cu O-Gu-NH N=N NHOCH; NH, 01 1 c1 CH1 CH:

' In the following table there are given further combinations prepared in accordance: with the invention.

' 7 .Oouplingqmiponent Diazotization component Shade o .c o O CH oH1 N,=N--N NH; Full reddish brown v CH:

O CH Gal l N NH1 Full reddish brown CIHI 00 4 CHI m N=NON NH, Middle brown CHI 1 l OCu-N H OCH in C333 N= N N H1 Middle brown 0-Gu-N H 0 OH.

CH: N=N N NH; Middle brown CH: I H: l

OCu0 O CH:

N=N NH: 'NH: Middlfl blOWI! OCu0 N=NQN Q GHQ-N Middle brown u /0- Cu- 0 O ClH QN=N NH: O-O ONH NH: Full black brown Coupling component Diawtiution component Shade 0u-NH 00H;

N=N 0H NH, Middle brown OCu--NH N=N -OH GHQ-NH; Middle brown OCuNH 00H i i 15 QN=NOOH NH; Middle brown o-ou -NH com. 2

N=N-C OH Q0 ONH NH, Black brown o-cu NH 00m 25 Q =N NH; NH, Middle brown c Q =NONH: CHiONH: Middle brown We claim: 7 ever, by the hydroxy group only when Y stands 1. Water insoluble azo dyestufis of the general for NH, R" stands for the radical of a diazotized formula: aromatic amine generally used in the manufac ture of ice colors R, R and R" being free from X-Mo-Y water solubilizing groups, X stands for a mem- 4.) wherein R stands for an aromatic radical ber selected from the group consisting of an stands for a radical of the benzene series capable oxygen atom and the group Y sitapds for a of coupling twice, which is substituted in a member selected from the group consisting of an sition meta to Y by a member of the group conoxygen atom and the group melding when i Sisting of an amino and hydroxy group, however, produfced on the fiber in general brown shades of 50 by the hydroxy group only when Y stands for g astnes.s propertles" NH, R stands for the radical of a diazotized f l Insoluble azo dyestuffs of the general aromatic amine generally used in the manufacormu fr ture of ice colors,.R, R and R" being free from water solubilizing groups, X stands for a mem- R N x ber selected from the group consisting of an oxygen atom and the group COO, Y stands for a member selected from the group consisting of v an oxygen atom and the group NH Me stands j herein R and R" stand for benzene radicals befor a metallic atom capable of yielding azo dyem fl m Water Solubilizing groups, x Stands 60 stuff complex compounds, and wherein the bridge 9 substltuent sjelected from the group X--Me--Y is attached to the nuclei in positions 818mg of the m 8mm and the hyqroxy ortho to the azo bridge, yielding when produced groupi and wheremfhe f OCu 'NH 15 on the fiber in general brown shades f good {ash tached to the nuclei in positions ortho to the azo mess propertiea bridge, yielding when produced on the fiber in 5,

Water insoluble d tuff of the general general brown shades of good fastness properties. formula; i 4. The water insoluble azo dyestuif of the for- R--N=N-R-N=NRf 11111131 0 Y OCu-0 wherein R stands for an aromatic radical, R N=N NH: Cl stands for a radical of the benzene series capable of coupling twice, which is substituted in a posi- N= tion meta to Y by a member of the group con- 7 sisting of an amino and hydroxy group, how- 01 CHI yielding when produced on the fiber a reddish brown.

5. The water insoluble azo dyestui! oi the formula:

wherein R stands for an aromatic radical, R. stands for a radical of the benzene series capable of coupling twice which is substituted in a position meta to Y by a member 01' the group consisting of the amino and hydroxy groups, however, by the hydroxy group only when Y stands for NH, R and R being free from water-solubilizing groups, X stands for a member selected Irom the group consisting of an oxygen atom and the group COO, Y stands for a member selected from the group consisting of an oxygen atom and the group NH, Me stands for a metallic atom capable of yielding azo dyestufl complex compounds, and wherein the bridge XMe--Y is attached to the nuclei in positions ortho to the azo bridge, and a compound selected from the group consisting of nitrosamines, diazoaminoand diazoimino compounds derived from aromatic amines generally used in the manufacture of ice colors.

12. Printing preparations containing as essential ingredients 9. compound of the general forwherein R stands for a radical of the benzene series which is free from water-solubilizing groups, Y stands for a member selected from the group consisting oi! an oxygen atom and the group NH, X stands for a member of the group consisting of the amino group and the hydroxy group, however, for the hydroxy group only when Y stands for the group NH, and wherein the bridge 0-Cu-Y is attached to the nuclei in positions ortho to the azo bridge, and a compound selected from the group consisting of nitrosamines, diazoaminoand diazoimino compounds derived from aromatic amines generally used in the manufacture of ice colors.

13. Printing preparations containing as essential ingredients a compound of the general formula:

wherein Z stands for a member selected from the group consisting of hydrogen, halogen, the nitro group and an alkyl group, Y stands for a member 01' the group consisting of an oxygen atom and the group NH and X stands for a member of the group consisting of the amino group and the hydroxy group, however, for the hydroxy group only when Y stands for the groupv NH, and a compound selected from the group consisting of nitrosamines, diazoaminoand diazoimino compounds derived from an aromatic amine suitable for the manufacture of ice colors.

'II-IEODOR KOLLMANN. EUGEN GLIETEN'BERG. 

